Computational fluid dynamics (CFD) has become a widely used tool for predicting hazardous scenarios. The present study aimed to assess CFD prediction applied to LPG containers under heating. Thus, two cylinders, each filled with propane or butane, were experimentally exposed to fire, and the pressure increment was recorded. The results were compared with those provided by a CFD method (Ansys Fluent). The limitations of the method are discussed, and a trend in the error increment and its relation to the reduced temperature increment are presented. The results obtained show that the computational method had a good agreement, with a relative error of 19% at a reduced temperature equal to 2. Furthermore, the method had a better fit with heavier alkanes, as the butane was less influenced by temperature overestimation compared with propane.